Laser-sensitive silver halide photosensitive material

ABSTRACT

A laser-sensitive photosensitive material, having improved photographic characteristics and being quick treatable, is disclosed which is prepared by use of a silver halide emulsion containing 0.001 to 0.04 mole of silver iodide per mol of silver halide, and contains in an emulsion layer or protective layer a compound having the general formula (I)   wherein Y1 and Y2 are individually a non-metallic atomic group necessary to form a nitrogen-containing heterocyclic ring of benzothiazole, benzoselenazole, naphthothiazole, naphthoselenazole or quinoline which heterocyclic ring may be substituted with halogen, lower alkyl or lower alkoxy; R1 and R3 are individually lower alkyl, carboxyalkyl, sulfoalkyl, hydroxyethyl, benzyl or sulfopropylthioethyl group; R2 is hydrogen or lower alkyl; X is an anion; n,n1 and n2 are individually 0 or 1; and n3 is 0 or 1 and 0 in case an intramolecular salt is formed; and at least one of compounds having the general formulas (II) to (VIII)   wherein Z is an atom or a group necessary to form a heterocyclic ring of thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, 3,3-dialkylindolenine, benzimidazole, thiazoline, pyridine, or quinoline; Q is an atom or group necessary to form a heterocyclic ring of pyrazalone, barbituric acid, thiobarbituric acid, isoxazolone, 3-hydroxythionaphthene or 1,3-indandione; R is a lower alkyl group or a carboxyethyl, sulfobenzyl or sulfophenylethyl group; R1 and R2 are individually hydrogen or chlorine, or an alkyl, alkoxy, amino, acylamino, alkylamino, dialkylamino or sulfonic group; X is an acid anion; m is 1 or 2; and n is 1,2 or 3;   WHEREIN Y IS A HYDROGEN, OR AN ALKYL, AMINO ACYLAMINO OR CARBOXYL GROUP; AND R3, R4, R5, R6, R7 and R8 are individually hydrogen or chlorine, or a hydroxy, alkoxy, alkyl, amino, acylamino, alkylamino, sulfonic or carboxyl group, provided that R7 and R8 may form a benzene ring, and   WHEREIN R8 is hydrogen or an alkyl group; R9 is hydrogen, or an acyl or alkoxycarbonyl group; and R10, R11, and R12 are individually hydrogen, or an alkyl or sulfonic group.

United States Patent [191 Nishina et al.

[111 3,847,621 (4373167. ii, i974 1 1 LASER-SENSITIVE SILVER HALllDEPHOTOSENSITIVE MATERIAL [73] Assignee: Konishiroku Photo Industry Co.

Ltd., Tokyo, Japan 22 Filed: Nov. 27, 1972 21 Appl. No.2 309,715

[30] Foreign Application Priority Data Primary ExaminerJ. Travis BrownAttorney, Agent, or FirmBierman & Bierman [57] ABSTRACT Alaser-sensitive photosensitive material, having improved photographiccharacteristics and being quick treatable, is disclosed which isprepared by use of a silver halide emulsion containing 0.001 to 0.04mole of silver iodide per mol of silver halide, and contains in anemulsion layer or protective layer a compound having the general formula(1) wherein Y and Y are individually a non-metallic atomic groupnecessary to form a nitrogen-containing heterocyclic ring ofbenzothiazole, benzoselenazole, naphthothiazole, naphthoselenazole orquinoline which heterocyclic ring may be substituted with halogen, loweralkyl or lower alkoxy; R and R are individually lower alkyl,carboxyalkyl, sulfoalkyl, hydroxyethyl, benzyl or sulfopropylthioethylgroup; R is hydrogen or lower alkyl; X is an anion; rm and n areindividually 0 or 1; and n is 0 or 1 and O in case an intramolecularsalt is formed; and at least one of compounds having the generalformulas (11) to (VIII) on H: (II) wherein Z is an atom or a groupnecessary to form a heterocyclic ring of thiazole, benzothiazole,naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole,benzoselenazole, naphthoselenazole, 3,3- dialkylindolenine,benzimidazole, thiazoline, pyridine, or quinoline; Q is an atom or groupnecessary to form a heterocyclic ring of pyrazalone, barbituric acid,thiobarbituric acid, isoxazolone, 3-hydroxythionaphthene or1,3-indandione; R is a lower alkyl group or a carboxyethyl, sulfobenzylor sulfophenylethyl group; R and R are individually hydrogen orchlorine, or an alkyl, alkoxy, amino, acylamino, alkylamino,dialkylamino or sulfonic group; X is an acid anion; m is 1 or 2; and nis 1,2 or 3;

wherein y is a hydrogen, or an alkyl, amino acylamino or carboxyl group;and R R R R R and R are individually hydrogen or chlorine, or a hydroxy,alkoxy, alkyl, amino, acylamino, alkylamino, sulfonic or carboxyl group,provided that R and R may form a benzene ring, and

5 Claims. No Drawings LASER-SENSITIVE SILVER HALIDE PHOTOSENSITIVEMATERIAL This invention relates to a laser facsimile photosensitivematerial for use in facsimile telegraphy using a laser.

According to the conventional facsimile telegraphic process, an electricsignal at the time of receiving has been converted into the intensity oflight by means of a crater tube. This process, however has suchdisadvantages that the crater tube is not only great in light loss butalso tends to undergo optical damage and is short in life.

In view of the above, there 'has recently been developed a process inwhich a laser, e.g., helium neon gas laser or semiconductor laser, isused in place of the crater tube.

In the case of facsimile telegraphy using such laser, a silver halidephotosensitive material to be used therefor is required to have variouscharacteristics. For example, the photosensitive material is required tobe sensitive to the wavelength of light emitted therefrom and highlysensitive even when exposed for to 10" seconds to a high luminancelight. Further, the receiving of facsimile telegraph is required to beconducted in an extremely short period of time. Accordingly, aphotosensitive material to be used therefor is also required to bedeveloped quickly, and thus the properties of the photosensitivematerial are of importance as well. Moreover, in order to make theworking efficiency favorable, there is required the use of a safe lightas bright as possible.

, The present invention provides a photosensitive material for use insuch laser facsimile telegraphic process. That is, the inventionprovides a quickly treatable laser facsimile photosensitive material,which is prepared by use of a silver halide emulsion comprising 0.1 to4.0 mole percent of silver iodide and 10' to 10' moles, per mole of saidemulsion, of a water-soluble iridium salt, and which contains in theemulsion layer or protective layer a compound having the general formulawherein Y and Y are individually a non-metal atom group necessary toform a nitrogen-containing heterocyclic ring of benzothiazole,naphthothiazole, benzoselenazole, naphthoselenazole or quinoline whichheterocyclic ring may have been substituted with a halogen atom, or alower alkyl or lower alkoxyl group; R and R are individually a loweralkyl, substituted alkyl, carboxyalkyl or sulfoalkyl group; R is ahydrogen atom or a lower alkyl group; X is an anion; n, n and n areindividually 0 or 1; and n is 0 or 1 and is O in case an intramolecularsalt is formed, and at least one of compounds having the generalformulas (II) to (Vlll),

Mi ..V wherein Z is an atom group necessary to form a heterocyclic ringof thiazole, benzothiazole, naphthothiazole,

15 oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenagple,naphthoselenagole, 3,3-dialkylindolenine, benzimidazole, thiazoline,pyridine or quinoline; Q is an atom group necessary to form aheterocyclic ring of pyrazolone, barbituric acid, thiobarbituric acid,isox- 2O azolone, 3-hydroxythionaphthene or l,3indandione; R is asubstituted or unsubstituted alkyl group; R and R are individually ahydrogen or chlorine atom, or an alkyl, alkoxy, amino, acylamino,alkylamino, dialkylamino or sulfonic group; X is an acid anion; m is lor 2;andnis 1,2 or 3,

Ra R0 QN=N R.

(VIII) wherein R is a hydrogen atom or an alkyl group; R is a hydrogenatom, or an acyl or alkoxycarbonyl group; and R R and R are individuallya hydrogen atom, or an alkyl or sulfonic group.

' The emulsion used in the present invention is a silver halide emulsioncontaining 0.3 to 4.0 mole percent of 3 silver iodide, and the amount ofbinder used in the emulsion is preferably 50 to 100 g. per mole of thesilver halide. The binder is used in said amount for such reason thatthe emulsion can be quickly dried at the time of quick treatment, and anemulsion containing more than 100 g. of binder is inferior in dryingproperty. An emulsion containing no silver iodide becomes low inspectral gamma of laser light (more than 500 my.) and is inferior insensitivity, and an image formed by use of such emulsion is inferior inquality. In case the emulsion is incorporated with about 10 to 10 moles,per mole of silver halide, of a water-soluble iridium salt, the emulsioncan be made higher in sensitivity. Typical examples of the water-solubleiridium salt used in the above case include Na lrCl and Na IrCl Concreteexamples of the compound having the aforesaid general formula (I) whichis to be added to t h e emulsion are as followsz am can 131- b231,bnnisol =CH-C=CH 2 5 l N eaN (crimson: (cmnsoi 58 Se U =CHC=CH \N N 5 So(I =CHC=CH a N N JJzHs JzHs Br =CHC=CH CH; 5 CH; N $N jHzh OaH (HDaSOa=CH-C=CH C1 J3EE! Cl N am WMXF FQ PFF. 4 9199 (8) s s I err-:011 N ZlzHa g I 2): OaH

(CHzhSOa CHC=CH H5020 \N (32m g Y -02H, immsoan 411103503 CHCH=CH I 10 Ne e I 13H: Br N 41113 e 15 CHCH=GH- 1 Q I H3O f I (cHnzswmnsoi N CHC=CHCH3 N/ 2H5 e z s I W Bhutan, s, *I

011,0 OCH:

=CH(CH=CH)2 crno 0CH: N @N alls (EH5 CH(CH=OH)r- 01 15 s s on, CH:

CH-(CH=GH)2 7 CH3 CH3 N N ea tingle o o H eHmco o 9 55 g GHC=CH iJhHuCH3 N N tinmsoaNa rinmsoa =CHC=CH 1 9 Calls N @N V dmcryon V I cmcmorr lon,

Ordinarily, the compound of the general formula (I) may be added at astage during or after the second ripening, and the amount thereof is 5to 500 mg., preferably 20 to 100 mg., per mole of silver halide. It isnot objectionable at all to use a mixture of compounds of the generalformula (I).

The compound of the general formulas (II) to (VIII) is incorporated intothe emulsion layer and/or protective layer. In case the compound isdesired to be incorporated into the emulsion layer, it may be added tothe emulsion after completion of the second ripening, and in case thecompound is desired to be incorporated into the protective layer, it maybe added at any stage before coating. The amount of the compound to beadded is 100 mg. to 3.0 g. per m Concrete examples of the compoundshaving the general formulas (II) to (VIII) are as follows:

. -crr,

I N-CH;

OzNn

The laser facsimile photosensitive material of the present inventionshows a high sensitivity when exposed for a short period of time (e.g.10 to seconds) to a high luminance laser, e.g. a helium neon gas laser(632.8 mp.) or semiconductor laser (690 mp), as is clear from theworking examples shown later. Moreover, it decreases the sensitivity ofunnecessary photosensitive wavelength region (400 to 600 mu), and can beused under a bright safety light, e.g., a green or yellowish greensafety light, to make it possible to enhance the working efficiency.Even when treated with a developer for high temperature quick treatment,the photo- CHSOC sensitive material can be quickly treated without anysubstantial formation of fog.

The present invention is illustratedbelow with reference to examples.

EXAMPLE 1 A silver iodobromide emulsion containing 0.5 mole percent ofsilver iodide was incorporated with 10 moles, per mole of the silverhalide, of Na h-C1 to prepare a sample A. On the other hand, theabovementioned silver iodobromide emulsion was used as it was as asample B. The two samples A and B were individually incorporated with 60mg., per mole of the silver halide, of the exemplified compound (8)having the general formula (I) and equally divided into two portions toform four emulsions. Two of the four emulsions thus formed wereindividually coated as they were on a support to prepare samples A-1 and8-1, and the other two of the four emulsions were individuallyincorporated with 9 g., per mole of the silver halide, of theexemplified compound 25 having the general formula (VII) and coated on asupport to prepare samples A-2 and B-2 (the amount of the exemplifiedcompound 25 was 0.5 g/m These samples were individually exposed for l0"seconds to a helium neon gas laser, developed and then measured indensity. On the other hand, the samples unexposed to the laser wereallowed to stand for 0 and 5 seconds under a 20W green safety light(Sakura Safety Light No. 5A- /z; produced by Konishiroko The exemplifiedcompound 25 was replaced by each of the exemplified compounds 8, l0, l5and 26 to ob- EXAMPLE 2 A silver chloroiodide emulsion containing 2 molepercent of silver iodide and 5 mole percent of silver chloride wasincorporated with 50 mg, per mole of the silver halide, of theexemplified compound (14) having the general formula (I), and thencoated on a support to prepare a sample. The thus prepared sample wasequally divided into two, and one of the divided samples was coated witha protective layer, which had been incorporated with the exemplifiedcompound 13 having the general formula (V) so that the amount of thecoated compound became 0.2 glm to prepare a sample C-l, while the otherof the divided samples was coated with a protective layer, which hadbeen incorporated with no such compound, to prepare a sample C-2. Thesesamples were subjected to the same measurement as in Example 1 to obtainthe results as set forth in Table 2.

Emulsions D and E prepared in the same manner as in the case of thesamples A and B used in Example 1 were individually incorporated withmg., per mole of the silver halide, of the exemplified compound (4)having the general formula (I), and then coated on a support to preparesamples. The samples were equally divided into two to prepare foursamples. Two of the four samples were individually coated with aprotective layer, which had been incorporated with a 1:1 mixture of theexemplified compound (4) having the general formula (II) and theexemplified compound (16) having the general formula (VI) so that theamount of the coated mixture became 0.6 g/m to prepare samples D-1 andD-l, while the other two of'the four samples were individually coatedwith a protective layer, which Table 3 Fog due to safety light secondseconds Density to laser light Sample What we claim is:

1. A quick treatable, laser-sensitive photosensitive material comprisinga silver halide emulsion containing 0.1 to 4.0 mole percent of silveriodide, which material contains in an emulsion layer or protective layera compound having the general formula (I),

.. wherein Y, and Y; are individually a non-metallic atomic groupnecessary to form a nitrogen-containing heterocyclic ring ofbenzothiazole, benzoselenazole, naphthothiazole, naphthoselenazole, orquinoline which heterocyclic ring may have been substituted with ahalogen atom, or a lower alkyl or lower alkoxyl group; R and R areindividually a lower alkyl, carboxyalkyl, sulfoalkyl, hydroxyethyl,benzyl or sulfopropylthioethyl group; R is hydorgen or a lower alkylgroup; X is an anion; n, and n are individually 0 or 1; n is I; and n is0 or 1 and 0 in case an intramolecular salt is formed; and

at least one compound having the general formula (II) to (VIII),

(III) 2a.. V, V V a (=0 H'CH) 21-1 5 5 l (IV) or quinoline; Q is an atomor group necessary to form a heterocyclic ring of pyrazolone, barbituricacid, thiobarbituric acid, isoxazolone, 3-hydroxythionaphthene or1,3-indandione; R is a lower alkyl, carboxyethyl, sulfobenzyl, orsulfophenylethyl group; R and R are individually hydrogen or chlorine,or an alkyl, alkoxy, amino, acylamino, alkylamino, dialkylamino orsulfonic group; X is an acid anion; m is l or 2; and n is 1,2 or 3;

Rs Ra -N= R4 R7 R9 wherein or an alltyl, amino, acylamino or carboxylgroup; and R R R R R and R are individually hydrogen or chlorine, or ahydroxy, alkoxy, alkyl, amino, acylamino, alkylamino, sulfonic orcarboxyl group, provided that R and R may form a benzene ring, and

N-Rs

(VIII) wherein R is hydrogen or an alkyl group; R is hydrogen, or anacyl or alkoxycarboxyl group; and R R and R are individually hydrogen,or an alkyl or sulfonic group.

2. A quick treatable, laser-sensitive photosensitive material comprisinga silver halide emulsion containing 0.1 to 4.0 mole percent of silveriodide, which material has 10 to 10 moles, per mole of the silverhalide, of water-soluble iridium salt incorporated therein, and containsin an emulsion layer or protective layer a compound having the generalformula (I),

wherein Y, and Y are individually a non-metallic atomic group necessaryto form a nitrogencontaining heterocyclic ring of benzothiazole,benzoselenazole, naphthothiazole, naphthoselenazole, or quinoline whichheterocyclic ring may have been substituted with a halogen atom, or alower alkyl or lower alkoxyl group; R, and R are individually a loweralkyl, carboxyalkyl, sulfoalkyl, hydroxyethyl, benzyl orsulfopropylthioethyl group; R is hydrogen or a lower alkyl group; X isan anion; n,n and n; are individually 0 or I; and n is 0 or 1 and 0 incase an intramolecular salt is formed; and

at least one compound having the general formula (II) to (VIII), V, a

wherein Z is an atom or group necessary to form a heterocyclic ring ofthiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole,naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, 3 ,3-dialkylindolenine, benzimidazole, thiazoline, pyridine, or quinoline; Qis an atom or group necessary to form a heterocyclic ring of pyrazolone,barbituric acid, thiobarbituric acid, isoxazolone,3-hydroxythionaphthene or l,3-indandione; R is a lower alkyl,carboxyethyl, sulfobenzyl, or sulfophenylethyl group; R and R areindividually hydrogen or chlorine, or an alkyl, alkoxy, amino,acylamino, alkylamino, dialkylamino or sulfonic group; X is an acidanion; m is l or 2; and n is 1,2

Ra Ru 2 3 -N=N R1 W Ru wherein Y is hydrogen, or an alkyl, amino,acylamino (VII) 7 or carboxyl group; and R R R R R and R are in- VIII)and at least one of the following compounds:

N S OaNa H OaNB 7 4. A laser-sensitive photosensitive materialcomprising a silver halide emulsion containing 0.1 to 4.0 mole percentof silver iodide, which material contains, in the emulsion layer ofprotective layer, a compound having the following chemical structure:

and a compound having the following chemical structure:

. 16 v 5. A laser-sensitive photosensitive material comprising a silverhalide emulsion containing 0.1 to 4.0 mole percent of silver iodide,which material contains, in the emulsion layer or protective layer, thefollowing compounds:

SOaH

dm-Q-s o

1. A QUICK TREATABLE, LASER-SENSITIVE PHOTOSENSITIVE MATERIAL COMPRISINGA SILVER HALIDE EMULSION CONTAINING 0.1 TO 4.0 MOLE PERCENT OF SILVERIODIDE, WHICH MATERIAL CONTAINS IN AN EMULSION LAYER OR PROTECTIVE LAYERA COMPOUND HAVING THE GENERAL FORMULA (1),
 2. A quick treatable,laser-sensitive photosensitive material comprising a silver halideemulsion containing 0.1 to 4.0 mole percent of silver iodide, whichmaterial has 10 8 to 10 6 moles, per mole of the silver halide, ofwater-soluble iridium salt incorporated therein, and contains in anemulsion layer or protective layer a compound having the general formula(I),
 3. A laser-sensitive photosensitive material comprising a silverhalide emulsion containing 0.1 to 4.0 mole percent of silver iodide,which material contains, in the emulsion layer or protective layer, acompound having the following chemical structure:
 4. A laser-sensitivephotosensitive material comprising a silver halide emulsion containing0.1 to 4.0 mole percent of silver iodide, which material contains, inthe emulsion layer of protective layer, a compound having the followingchemical structure:
 5. A laser-sensitive photosensitive materialcomprising a silver halide emulsion containing 0.1 to 4.0 mole percentof silver iodide, which material contains, in the emulsion layer orprotective layer, the following compounds: